Metalizable azo dyestuffs



Patented Nov. 10, 194-2 UNir 'EES a T E O F F I C E METALIZABLE AZO DYESTUFFS No Drawing. Application December 20, 1940, Se-

rial No. 371,057. 1936 7 Claims.

This application is a continuation-in-part of my application for patent Serial No. 319,810, filed in the U. S. A. on February 19, 1940, which is itself a continuation-in-part of my application for patent Serial No. 166,021, filed in the U. S. A. on September 27, 1937, and in Switzerland on October 3, 1936.

According to this invention valuable aZo-dyestufis are obtained by causing a diazo-compound of the benzene and naphthalene series which contains in ortho-position to the diazo-group a substituent which is capable of forming stable lakes with the aZo-group formed, such as an orthohydroxy or ortho-carboxy-diazo compound to react with a 1-aryl-5-pyrazolone which itself is obtainable by condensation of a fi-carbonyl-carboxylic acid ester with a hydrazine of the general formula in which y represents a CI-I=CII-groupor a CH2CH2-group and 2 represents a group which is formed by reduction of a nitro-group in combination with a condensation, such as an amino-group substituted by the residue of an organic acid; The new azo-dy'estuffs thus obtained are distinguished by their affinity for vegetable fibres, such as cotton, flax, ramie, and for fibres of regenerated cellulose, such as rayons, for example viscous rayon or cuprammonium' rayon and by the capability of the dyeings thus obtained being-after-treated with agents yielding metal, whereby their fastness properties, particularly their fastness to light and in certain cases also their fastness to washing may be improved considerably.

Among the ortho-hydroxy and ortho-carboxydiazo compounds which come nito consideration for the preparation of the azo-dyestuffs forming the parent materials of the invention there may be named quite generally those derived from ortho-aminophenols or ortho-aminonaphthols or from ortho-aminocarboxylic acids of the benzene or naphthalene series, for example 1-hydroxy-2- S 0311 S 03H In Switzerland October 3,

aminobenzene, l-hydroxy-Z-amino-4-ch1orbenzene, 1-hydroXy-2-amino-4-nitrobenzene, l-hydroxy-Z-amino-5-nitrobenzene, 1 hydroxy 2 amino-4 6 dinitrobenzene, 1-hydroxy-2-amino- 5-nitro-6-ch1orbanzene, I-hydroxy-Z-amino-4- methyl-benzene, 1-hydroxy-2-amino- I-nitro-G- chlorbenzene, l-hydroxy-Z-amino 4 nitrobenzene-6-sulfc'nic acid, 1-hydroxy 2 -amino fi-nitrobenzenel-sulfonic acid, 1-hydroxy-2-aminobenzene e sulfamide, l-hydroxy 2 aminonaphthalene-zB-disulfonic acid, Z-hydroxy-l-aminonaphthalenel-sulfonic acid, ,2-hydroxy-1-amino- 6-nitronaphthalene-4-su1fonic acid, l-aminobenzene-Z-carboxylic acid, l-aminol-chlorbenzene- Z-carboxylic acid, 1-amino-4-nitrobenzene-2-carboxylic acid,-1-amino-4-benzolamino-2-carboxylic acid, 4-amino 3 carboxylic-azobenzenel-sulionic acid, aminosulfobenzoic acid (NI-12:1, COOHzZ, SO3HI4) 2-aminonaphthalene-3-carboxylic acid, and so on.

Among the p-carbonyl-carboxylic acid esters available for preparing the 1-aryl-5-pyrazo1ones which can be used for the synthesis of the parent dyestuffs. there may be named formyl acetic acid esters, furthermore fi-keto-carboxylic acid esters, such as ethyl-aceto-acetate, ethyloxal acetate, ethylbenzolacetate, terephthaloyldiacetic acid ethyl ester, and so on. Among the hydrazines which likewise areused for preparing the l-aryl- 5-pyrazolones used for the synthesis of the parent dyestuffs there may be namedsuch products as:

group to the NHz-group and subsequent condensation, for example with a halogen compound which converts the NHz-group into a NH- (ll-bgroup in which a stands for metalloid whose atomic weight is not less than 14 and not greater than 16, and 1) stands for an organic residue of the aliphatic, aromatic, cycloaliphatic, heterocyclic, araliphatic series and so on. Such products constitute acyl derivatives or the amidines which chemically are closely related thereto. As is known, the introduction of such residues into intermediate products or dyestuffs increase the affinity for vegetable fibre. Such residues can be introduced by acylation, for example by treatment with benzoyl chloride, phenylacetyl chloride, cinnamyl chloride, succinyl chloride, butyryl chloride, hexaliydro-benzoyl chloride, furanecarboxylic acid chloride, benzimino ether, and particularly by treatment with phosgene or thicphosgene or by treatment with heterocyclic products of the nature of amidine halides, such as cyanuric acid chloride, cyanuric acid bromide, tribromopyrimidine, 2 fi-dichlorol-methylpyridine, dichloroquinazoline, and so on.

Particularly valuable products result when the condensation is conducted in such a manner that the residue b is so constituted that it contains an azochromophore or is adapted to couple with diazo compounds to produce azo-dyestuffs. There are thus obtained 1-aryl-5-pyrazolones in which the aryl residue has the general formula SOaH $03 II 50311 80:11 O

SOSH

SOsH

SOQH

QCH

CH=OH SQaH SOsH OH=CH SOaH SOaH From a comparison of the pyrazolone nuclei in which R stands for an aromatic nucleus of of the products of the Formulae 1-7with those 55 the benzene or naphthalene series, 0: stands for of the products resulting from the reduction of an ()H- or a COOH-group which stands in a nitro-group together with a condensation ortho-position to the -N=N-'group, 2; stands, for shown in Formulae 5-17, all of which are given instance, for hydrogen, alkyl, aryl, COOH or by way of'example, it is evident how numerous COOR (R=alkyl), y for a CH CH- or a are the intermediate products for making the 60 CH2-CH2-group, andz foraNOzor Nl-lz-group, azo-dyestuffs forming the invention; regard must and then to proceed with the conversion of the nitroor amino-group.

further be had to the fact that the aryl residue of the pyrazolones may belong either to the stil- The combination of the aforesaid coupling components and diazotized ortho-hydroxylated first to convert the l-aryl-5-pyrazolonesfrom' or ortho-carboxylated diazotization components the aforesaid nitroor amino-hydrazines by couplingwith one of the diazo compounds already bene or to thedibenzyl series. It is also possible to produce azo-dyestuffs proceeds; as is usual for pyrazolones, in an acid or an alkaline medium. referred to into azo-dyestuffs of the general As will be apparent from the foregoing formulae formula:

of the coupling components, besides the formation of't'he pyrazolone=azo-dyestufi a further'azo- 'dyestufi formation may occur, for example with the residue of one ofthe aminophenolor aminohydroxynaphthalene derivatives named (see for instance Formulae 13 and 20). In this case it is possible to prepare as may be desired mixed dyestuffs in respect of the diazotization components, Reference must also be made to the further possince, apart from the difierent coupling powers sibilities aflorded by the diazo components hereof the diazo components, the coupling powers of inbefore mentioned and the formulae of the couthe various residues of the coupling components pling components given by way of example.

are also different. Thus, quite generally the diazotized ortho-aminocarboxylic acids couple cordingly azo-dyestufls of the general formula more easily than the diazotized ortho-aminohydroxy compounds and the pyrazolones more easily than the 1-hydroxynaphthalene-3-sulfonic T acid residues. Thus, by combining 1 mol of di- 10 RN=NPy y Nv-N-R1N=NRz azotized 1-amino-benzene-2-carboxylic acid in I an acetic acid medium with 1 mol of the com- SOaH SOsH pound of the Formula 19, and then combining the mono-azo-dyestufi further in an alkaline medium with 1 mol of diazotized l-hydroxy-Z- 15 in which :1: stands for a substituent in orthoaminobenzenei-sulfonic acid, there is produced position to the N=N-group which is capable of a dyestufl of the formula: forming complex compounds with metals, Py

OOH H 1 sou; SOaH The new azo-dyestufis have for instance the following formulas:

-C HI H:

The dyestuffs of the present invention are ac-- H H S 0311 and in 4-position with the aZo-residue, 3 stands for a CH=CH- or a CH2-CI-I2-group, v for a member of the group consisting of CO and a connecting member consisting of a heterocyclic six membered nucleus which consists of at least 3 and at the most 4 carbon atoms and of at least 2 and at the most 3 nitrogen atoms, the nitrogen atoms being separated from one another by at acetic acid medium'with 45.1 parts of the 3- met-hyl-5-pyrazolone of the formula The dyestufi is isolated, dissolved in 1000 parts of water, containing an excess of sodium carbonate, and the solution is treated with phosgene at 4050 C. When thistreatment is ended, that least one carbon atom, one carbon atom adjais 5 When a ee amino-group is no longer cent to one nitrogen atom being linked by a present, the dyestufl is isolated and dried. It-is a yellow powder which dyes cotton fast yellow shades which become very fast to light by aftercQppering. The dyestuif corresponds to the forgroup to the radical containing the pyrazolone mula nucleus and another carbon atom adjacent to one 3 nitrogen atom being linked by the which in particular is responsible for the shade of the dyestuffs, their afiinity for vegetable fibers, and the high fastness to light of the dyeings after-treated with metal, as will be evident from a comparison of the properties of the individual products described in the examples which follow. I

When prepared in substance the new products constitute in the dry state yellow to brown or blackish powders which are soluble in water to yellow to orange, brown, greenish, olive and blackish solutions from which they are adsorbed by cellulose fibres yielding dyeings of similar shades if after-treated with agents yielding metal, which are distinguished by their excellent properties hereinbefore referred to. Details in respect of the manufacture of such dyestuffs and of their properties will be found in the following examples, the number of which could be multiplied as desired. The parts in the examples are by weight.

In all the examples, the formulas given represent the products in their free states.

Example 1 13.7 parts of l-aminobenzene-z-carboxylic acid diazotized in the usual manner and coupled in an S 0 H S 0211 I 0 parts of 1-aminobenzene-2-carboxylic acidwith 45.3 parts of the 3-methyl-5-pyrazolone of the formula CH (I) S 03H S 03H and treating the dyestufi with phosgene there is obtained a dyestuff which, when dried, consti tutes a yellow-brown powder and dyes cotton yellow shades, resembling in shade and properties those of the stilbene product.

Fast yellow shades with a somewhat orange hue are obtained by dyeing with the non-metallized dyestufi in the manner usual for dyeing with direct dyestuffs and then after-coppering or aftertreating the dyeing with a nickel salt. By treating with an iron salt a dyeing prepared with the dyestufi' there is obtained a dull yellow shade, by treatment with a cobalt salt a yellow shade, with a chromium salt a somewhat greenish-yellow shade and with a manganese salt a yellow shade.

Example 2 45 parts of the 3-methyl-5-pyrazolone of the formula N CH=CH NH: H2 0 l l I] s 03H s 03H 0 or of the formula (IJHs O=N /N- CH2-CH3 NH, Hz 0 i (ll) SOaH SOaH are dissolved in 500 parts of water and 11 parts of sodium carbonate and converted into the corresponding urea by the introduction of phosgene having similar valuable properties are obtained. at a temperature of 4050 C. When the free The formula of a dyestuff of this group is for amino-group has disappeared the urea is isoinstance lated.

coon coon C=N N=o -ooorr H000- N OH=OH NCN -OH=CH N I ll 1 N=NCC H H g OC-N=N- S0311 soul S0311 0311 H 0 0 11 46.2 parts of the urea thus obtained are dissolved in water together with the quantity of sodium carbonate necessary for forming the sodium salt, 13.6 parts of sodium acetate are added 5 and the solution is coupled in the usual manner with a solution of the diazo compound from 13.7 parts of 1-aminobenzene-2-carboxylic acid.

1 h di a eared t e tfitit 221m?iiifiri titfi aminfifis, gently W similar dyestuffs n d if t heated and filtered after the addition of common grow? of PTea IesidU-e is replaced by hetersalt. The dyestuff thus obtained shows the same ocychc am1d}ne'11ke nucleus- Such a P behaviour as the dyestuff described in the precedcan be obtained for example, by ing example. The replacement of phosgene by Ifarts of the 3-methyl-5-pyrazolone named in the thiophosgene leads to a similar product. So also first paliagraph of thls exfimple a fine'a1que0u5 dyes the replacement of the l aminobenzene z suspension of 18.4 parts or cyanuric chloride, care carboxylic acid by the l-amino--chlorobenzenebemg taken to W the reaqtlon mass J Z-carboxylic acid, by 1-amino-4-nitrobenzene-2- w by the addltlon of a P 50111- carboxylic acid, by 1-amino-4-methylbenzene-2- when no m Sodlum carbonate 1S 0011- carboxylic acid or by sumed the secondary condensation product from z carboxylic acid 2 mols of the pyrazolone and 1 mol of cyanuric If there is used as parent material for making chloride has been formed. If required, this seethe metamferous dyestuff the g 5 ondary product can be converted into a tertiary razolone of the formula condensation product by replacing the remaining chlorine atom in the cyanuric ring by treatment (IIOOH S0311 $0311 with 9.3 parts of aniline in known manner. 11 C=N I now the sodium salt from 53.5 parts of this condensation product is combined with the diazo H compound from 13.7 parts of l-aminobenzene-2- H carboxylic acid there is obtained a dyestuff which 0 resembles the azo-dyestuff of Example 1. The

obtainable by condensation of the correspondafter-copp e dye ng on cotton shows for ining hydrazine with oxalacetic ester or its sodium stance yellow shades very fast to light. The forcompound and saponification of the carboxylic mula of the dyestuff is therefore:

HOOC

ester group, or the 3-pheny1-5-pyrazolone of the formula If in the preparation of such dyestufis or of the condensation products from amino-aryl-pyrazo- S0311 lone and cyanuric chloride from which they are G=N I 1 derived the 18.4 parts of cyanuric chloride are C =CH ONH, replaced by 11.5 parts of 2:6-dichlorol-methylpyrimidine or 19.9 parts of dichloro-quinazoline n or 21.4 parts of phenylchlorotriazine, dyestufi's 0 having very similar properties are obtained. The (obtainable from benzoylacetic ester), dyestuffs formula of such a dye ufi s H o H000 00011 (11H,

It dyes cotton yellow tints which become fast to nolisreplacedbybneofitssubstitution products, light by after-coppering. If half of the l-aminosuch as 4-chloro-2-amino 'l hydroxybenzene or benzene-2-carbo-Xylic acid which isemployed for 4- or 5-nitro-2-amino-1-hydroxy-benzene, or by the preparation of this dyestuff is replaced by the one of the other ortho-hydroxyamino compounds corresponding quantity of L-amino-Z-hydroXyof the benzene or naphthalene series named in benzene-*5-sulfonic acid there i obtained a dyelithe introduction, dyestuffs are obtained which stuff of the formula; can like wise'be converted on the fiberinto com- H; I only SO3H SOaH so n soda 1 COOH I I I I I I 011 l N CH.OH N O .CH.CH. N l I N=N-- 0 HO N o N=N I II I H o 0 H HOsS which dyes cotton yellow-orange tints which beplex copper or other metal compounds. In this come fast tolight by after-coppering. connection the following may be said.

Exam 1e 3 '20 Whilst replacement of th l-amino-z-carbo-x- V p ,ylic ;acid by the; aforesaid substitution products 92:8'parts of'the 3-methyl-5-pyrazolone of the of this body influences.the shade of the final dyeformula. stufi'only to a smallextent, substantial displace- YCH: I $113 J=N I p I /N=C H2 0 H g H I 0-0112 ll SOaH S0311 S0311 SOaH H o o in the form of the neutral sodium salt are dis-' ment of the shade can be obtained by suitable solved in water together with the necessary quanselection of the ortho-hydroxy-diazo compound,

tity of sodium carbonate, and after addition of whereby, for instance, products which dye or- 13.6 parts of crystallized sodium acetate the soluange, to brown-yellow and reddish shades can be $1 i boupled with the diazo compound from "jp're pared. Thus for example, thecopper com- 1'3.'7 .parts of 1-aminobenZene-2-carboxylic acid. pound of the product from 1 mol of the pyrazo- After some time 1.1.6 partsof sodium carbonate lone-urea derivative of the first paragraph of this are added to the suspension of the mono-azoexamp'1e with 1 mol of diazotized 1-amino-2- dyestuff. The mono-azo-dyestuii thereupon discarboxylic acid and 1 mol'of diazotized S-nitro solves and is then further coupledwith adiazo Zaamino l hydroxy benzene, when formed on the solution preparedas usual'from 18.9 parts of 1- fiber, dyes'brown-yellow shades. Replacement of -hydroxy z-aminobenzene-4-sulf-onic acid. The the 5-nitro-2-amino-l-hydroxybenzene derivadyestuff is isolated by salting-out, filtered with M tive by diazotized 1amino-2-hydroXynaphthal suction .and=dried. When dry it is a dark ,brown ene-l-sulfonic acid leads on the fiber to a copper powder .whichdyescotton and similar fibres yelcompound which dyes reddish-brown shades. low-brown shades which become veryfast tolight If in this example the 3-methyl-5-pyrazolone whenafter-coppered. is replaced by the corresponding 5-pyrazolone- Thedyestufi .thus obtainedJhas the ,formula 3-carboxylic acid there are obtained analogous E (IJHQ O=N N=O OOOH OH L l I i 1 0 H g CCN=N 1 II S0311 S0311 SOsH 1 03H II I H 0 0 H 1 By treating the dyestuff of the above formula dyestuffs which, especially if after-coppered on on the fiber with agents yielding copper, there are the fiber, .dye vegetable fibres shades which are obtained brown-yellow shades. With other metextremely fast :tolight. Furthermore, the deals than copper, such as salts of manganese, iron, rivatives' of the other l-aryl-5-pyrazolones r cobalt, nickel, chromium, and so on, there are ferred .to'in Example 2 lead to similar products. obtained similar yellow-brown shades. If in the preparation of the dyestuffs from the If in'the-present Example the l-aminobenzener urea pyrazolone derivatives of the presentex- Z-carboxylic acid is replaced by a substituted ample the 1-aminobenzene-2ecarboxylic acid is anthranilic acid such as l-amino-4-chlorobenalso replaced by an ortho-aminophenol, dyestuffs zene-2-carboxylic acid or l-aminol-nitrobendyeing darker shades are obtained. Thus, the zene-2-carboxylic acid and the ortho-aminophedyestuffof the formula 01 coon I I c0011 01 I G=N\ /N=C I I -N=,Nc-o H 0 H I l '0-0N=N- I ll S0311 S0311 sour $0211 I;

H H H if treated on the fiber with agents yielding copper, dyes cotton brown-red.

Example 4 13.7 parts of 1-aminobenzene-2-carboxylic acid are dissolved in 30 parts of concentrated hydrochloric acid and after addition of ice the solution is diazotized at C. with a concentrated aqueous solution of '7 parts of sodium nitrite. This diazo solution is poured into a solution of 21 parts of sodium carbonate and 45.1 parts of the pyrazolone of the formula in 500 parts of water.

The whole is heated to 40 C. and stirred for some hours until the condensation is finished, whereupon 5 parts of sodium carbonate dissolved in little water and 18 parts of aniline are added to the mixture, which is then further heated for 1 hour at 90 C. 6 parts of sodium carbonate are then strewn into the mixture and the dyestuff is salted out, filtered and dried. It dyes cotton yellow tints.

The aminoazo-dyestuif of the formula (3H3 C=N i 3 4. \O N=N H2N H is obtained in the following manner:

19.5 parts of finely pulverized 2-amino-7-nitr0- benzthiazole are suspended in little ice water and 30 parts of concentrated hydrochloric acid, and

the suspension is diazotized at C. with a concentrated aqueous solution of 7 parts of sodium nitrite. The diazo paste thus obtained is poured into a solution of 16 parts of sodium carbonate and 25.4 parts of 1-phenyl-3-methy1-5-pyrazolone-4-sulfonic acid in 150 parts of water and little ice. When coupling is complete there are added 40 parts of crystallized sodium sulfide, the whole is heated for two hours at 60 C., and the aminoazo-dyestuff is salted out.

Example 5 66.5 parts of the sodium salt of the monoazodyestufi from 1-aminobenzene-Q-carboxylic acid and the pyrazolone of the formula are dissolved in 500 parts of water and so much ice is added that the temperature falls to 0 C. A suspension of 18.4 parts of cyanuric chloride in ice water is poured into this solution and the whole is stirred for about 1 hour until complete condensation has taken place. It is then neutralized with 5 parts of sodium carbonate. 6114 parts of the sodium salt of the aminoazo-dyestufi of the formula N=NC-C are dissolved in 500 parts of water and this solution is poured into the condensation product. The solution is heated for some hours to 40 C. until no free amino-group can be detected. A solution of 5 parts of sodium carbonate in water and then 18 parts of aniline are added and the whole is heated to C. 6 parts of sodium carbonate are strewn into the mixture and the dyestuff thus obtained is salted out, filtered and dried. It dyes cotton yellow orange tints.

The aminoazo-dyestufi of the above formula is prepared as follows:

33.5 parts of the azirnide-sulfonic acid of the formula (obtainable in known manner by oxidation of the azo-dyestuif from para-nitrodiazobenzene and meta-phenylenediamine sulfonic acid) are dissolved in parts of water and 14 parts of caustice soda solution of 30 per cent. strength. 7 parts of sodium nitrite are added to this solution and the whole is poured into a mixture of 40 parts of concentrated hydrochloric acid and ice, whereupon it is stirred at 10 C. until diazotization is complete. 25.4 parts of l-phenyl-3-methyl-5- pyrazolone-4'-sulfonic acid are dissolved in a solution of 16 parts of sodium carbonate in 150 parts of water and little ice and the diazo paste is then SOaH I NHz added to this solution while stirring well. When coupling is complete there are added 40 parts of crystallized sodium sulfide. The whole is then heated for 2 hours at 60 C. and the aminoazodyestuff is salted out.

What I claim is:

1. The azo-dyestufis having in the free state the general formula I l H H SOsH SOaH and in 4-position with the azo-group, 1; stands for a connecting link of the group consisting of --'CI-I=CH- and -CH2CH2, v for a member of the group consisting of CO and a connecting member consisting of a lieterocyclic six membered nucleus which consists of at least 3 and at the most 4 carbon atoms and of at least 2 and at the most 3 nitrogen atoms, the nitrogen atoms being separated from one another by at least one carbon atom, one carbon atom adjacent to one nitrogen atom being linked by a group to the radical containing the pyrazolone nucleus and another carbon atom adjacent to one nitrogen atom being linked by the group to R1, R1 standing for a complex consisting of at least one aromatic nucleus and at least one heterocyclic nucleus, and R2 for an aromatic nucleus selected from the group consisting of aromatic nuclei of the benzene and naphthalene series, which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton yellow to orange, brown and olive tints which become particularly fast to light by after-coppering.

2. The azo-dyestuffs having in the free state the general formula SOKH in which R stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, an stands for a lake-forming group in ortho-position to the N=Hgroup, Py stands for the radical of a -pyrazolone which is combined in l-position with the radical s03]; SO3H and in 4-position with the azo-group, v for a member of the group consisting of CO and a connecting member consisting of a heter-ocyclic six membered nucleus which consists of at least Q Qi FQQ r v H H I O H S 0 3H S O 3 and at the most 4 carbon atoms and of at least 2 and at the most 3 nitrogen atoms, the

nitrogen atoms being separated from one another aromatic nuclei of the benzene and naphthalene F series, which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton yellow to orange, brown and olive tints which become particularly fast to light by aiter-coppering.

3. The azo-dyestufis having in the free state the general formula S0311 SOaH H H v in which R. stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, a: stands for-a lake-forming group in ortho-position to the N=Ngroup, Py stands for the radical of a 5-pyrazolone which is combined in l-position with the radical l H H S 03H S 0311 and in e-position with the azo-group, v for a member of the group consisting of CO and a connecting member consisting of a heterocyclic six membered nucleus which consists of at least 3 and at the most 4 carbon atoms and of at least 2 and at the most 3 nitrogen atoms, the nitrogen atoms being separated from one another by at least one carbon atom, one carbon atom adjacent to one nitrogen atom being linked by the group to the radical containing the pyrazolone nucleus and another carbon atom adjacent to one nitrogen atom being linked by the group to the complex R1, R1 standing for a complex consisting of at least one aromatic nucleus and one pyrazolone nucleus, and R2 for an aromatic nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton yellow to orange, brown and olive tints which become particularly fast to light, by after-'coppering.

4. The azo-dyestuffs having in the free state the general formula in which R1 and R2 stand for nuclei of the group consisting of aromatic nuclei of the benzene and naphthalene series, a: and a stand for lake-forming groups in ortho-position to the N=N groups, Py and A stand for radicals of 5-pyrazolones which are combined in l-position with the radical and in 4-position with the azo-groups, y stands for a connecting link of the group consisting of CH=CH and CH2-CH2, and v for a member of the group consisting of CO and a connecting member consisting of a heterocyclic six membered nucleus which consists of at least 3 and at the most 4 carbon atoms and of at least 2 and at the most 3 nitrogen atoms, the nitrogen atoms being separated from one another by at least one carbon atom, two carbon atoms adjacent each to one nitrogen atom being linked by jacent each to one nitrogen atom being linked the by the N .N i 5 i groups to the radicals groups to the radicals CH=CH s 03H s 03H S0311 S0311 which products form yellow to brown powders,

dissolve in water to yellow to orange, brown and which products form yellow to brown powders, olive solutions, and dye cotton yellow to orange, dissolve in water to yellow to orange, brown and brown and olive tints which become particularly olive solutions, and dye cotton yellow to orange, fast to light by after-coppering.

brown and olive tints which become particularly 6. The dyestuifs having in the free state the fast to light by after-coppering. formula 7 i RiN=NPyor =cH- -1 -v-1 I :y oH=oH-OPyN=NR, H H 03H S0311 SOaH sonar 5. The azo-dyestufis having in the free state in which R1 and R2 stand for nuclei of the benthe general formula zene series, a: and 2 stand for lake-forming i i R1N=NP QoH=0HIfv1 0H=CHQA-N=NR2 H H S0311 S0311 S0311 SOGH in which R1 and R2 stand for nuclei of the group groups in ortho-position to the -N=N-groups, consisting of aromatic nuclei of the benzene and 2; stands for a connecting member consisting of a naphthalene series, a: and 2 stand for lake-form- 1:35 triazine compound, two carbon atoms of the ing groups in ortho-position in the N=N triazine nucleus being each linked to the groups, Py and A stand for radicals of 5-pyrazolones which are combined in l-position with l the radical H group, Py stands for the radical of a 5-pyrazolone which is linked in 1 position to the radical SO H S0 H SOaH SOQH 3 s and in 4-position to the azo group, which 'products form yellow to brown powders, dissolve in and in 4-position with the azo-groups, and 1) water to yellow to orange and brown solutions for a member of the group consisting of CO and and dye cotton similar tints which become fast a connecting member consisting of a heterocyclic to light by after-coppering. six membered nucleus which consists of at least 7. The azo-dyestuff having in the free state the 3 and at the most 4 carbon atoms and of at least formula 2 and at the most 3 nitrogen atoms, the nitrogen :15 which yields on the vegetable fiber yellow tints atoms being separated from one another by at which become fast to light by after-coppering, least one carbon atom, two carbon atoms ad- MAX SCHMID. 

